CN101643556A - Elastomeric compositions comprising hydrocarbon polymer additives having improved impermeability - Google Patents

Abstract

An elastomeric compositions having improved impermeability is disclosed. The cured elastomeric composition may comprise at least one C 4 -C 7 monoolefin elastomer, a hydrocarbon polymer additive, anda clay. In some embodiments, the cured elastomeric composition has a permeation coefficient at 40 DEG C of 90 cc*mm/(m 2 -day) or less. In some embodiments, the elastomeric composition is substantially free of naphthenic oil.

Description

The impermeable elastic composition that comprises hydrocarbon polymer additives with improvement

Technical field

[0001] the present invention relates to have the impermeable elastic composition of improvement.More specifically, the present invention relates to have the impermeable vulcanized elastomer composition that comprises hydrocarbon polymer additives of improvement.

Background technology

[0002] elastic composition is used for many application, comprises flexible pipe, belt, footwear component, vibration insolation means, tire and tyre assembly such as tyre surface, liner and tyre sidewall.The selection that is used for the composition of elastic composition commercial formulation is depended on the character of requirement, application and is used the balance of end-use.

[0003] for example, in tire industry, the balance particularly important of the performance in the working properties of unprocessed in tire plant (unvulcanized) composition and the use of vulcanized rubber tire matrix material.The ability of improving the weather resistance of the tire that is used for multiple condition for example is agricultural tire, plane tyre, bull dozer tire, heavy truck tire, mining tire, motorcycle tyre, Medium Truck tire and the requirement of passenger tyre institute, and keeping not simultaneously, the easy degree of vulcanized elastomer composition processing characteristics also has significant importance.In addition, still exist under the processing characteristics that does not influence vulcanized elastomer composition not, when keeping or improving the physicals of vulcanized elastomer composition, improve resistance to air loss, flexing fatigue character and elastic composition to adjacent tyre assembly adherent target.

[0004] traditionally, various processing oils such as naphthenic, paraffinic and the many tire components of aromatics oil adding are processed to help mixed ingredients.Naphthenic oil is owing to its processing effectiveness and useful auxiliary character for example are preferred for the tire flap mixing material with elastomeric consistency based on iso-butylene.Yet though the processing oils of these routines has been improved processing characteristics, this benefit comprises that for various other character resistance to air loss may have undesirable influence.

[0005] common, the feed composition and the material that are used for the tire compounding are influential to all tyre performance variablees, any surrogate of therefore conventional processing oils must be compatible with rubber, do not influence vulcanization rate, is easy to disperse, have the performance of economic benefit and not negative impact tire in the tire mixed ingredients.This is for the tire flap and the tube particularly important that wherein show in the permission limit that performance must remain on regulation.For example a small amount of increase of tire flap mixing material 300% modulus can cause fatigue resistance to reduce and cracking reaches the loss that correspondingly causes tyre last.And for the elastic composition as air shield (air barrier), particularly importantly any benefit of mixed ingredients processing characteristics can not be the loss of composition air hold facility.

[0006] because oils such as rubber grade naphthenic oil or paraffinic oils tend to improve the perviousness of elastic composition, halogen butyl rubber has been used for the tire flap mixed ingredients to help improving air retention (capacity).Pressuretightness further improvement reaches by clay being added elastomerics formation " nano composite material ".Yet, still have demand for the elastic composition of air hold facility with excellent machinability and improvement.

[0007] because for special performance characteristic with many tire compoundings and through engineering approaches, it is desirable that any surrogate of traditional treated oil keeps tyre performance feature such as rolling resistance, tractive force and wear hardness.The improvement of air retention (capacity) matter can be allowed in the weather resistance of the maintenance of the improvement of tire length of life rolling resistance performance, improvement and lower tire working temperature, therefore still has the demand for the impermeable tradition processing oils surrogate in tire and tire flap mixing material of the tire flap of allowing useful mixing material processing characteristics and improvement.

Summary of the invention

[0008] on the one hand, present disclosure relates to a kind of elastic composition.This elastic composition comprises at least a C ₄-C ₇Monoolefm elastomer, hydrocarbon polymer additives and clay.

[0009] on the other hand, present disclosure relates to vulcanized elastomer composition.This vulcanized elastomer composition comprises at least a C ₄-C ₇Monoolefm elastomer, hydrocarbon polymer additives and clay.In some embodiments, vulcanized elastomer composition has at 40 ℃ of following 90cc*mm/ (m ²-day) or littler, perhaps 80cc*mm/ (m in other embodiments ²-day) or littler permeability coefficient.

[0010] further, present disclosure relate to a kind of air shield, as tire flap, the inner tube of a tyre or flexible pipe.This air shield comprises elastic composition, and this elastic composition passes through at least a based on C ₄-C ₇Monoolefine elastomerics, at least a filler, at least a clay, at least a hydrocarbon polymer additives and at least a vulcanizing agent bonded method and prepare.Then the bonded component is vulcanized.In some embodiments, this air shield has at 40 ℃ of following 90cc*mm/ (m ²-day) or littler or 80cc*mm/ (m in other embodiments ²-day) or littler permeability coefficient.

[0011] in one embodiment, and combine with any above-mentioned disclosed aspect or embodiment, the scopes that hydrocarbon polymer additives can 10 to 40phr exist.Hydrocarbon polymer additives preferably comprises the ring-type component, and more preferably comprises Dicyclopentadiene (DCPD).Hydrocarbon polymer additives can have by ASTM E28-99 to be measured at about 115 ℃ of softening temperatures that arrive in about 130 ℃ of scopes.

[0012] in preferred embodiments, and combine with any above-mentioned disclosed aspect or embodiment, this elastic composition and/or air shield are substantially free of naphthenic oil.

[0013] in another embodiment, and combine, based on C with any above-mentioned disclosed aspect or embodiment ₄-C ₇The elastomerics of monoolefine can be selected from isoprene-isobutylene rubber, halogenated butyl rubber, branching (" star-branching ") isoprene-isobutylene rubber, halogenated star-branched butyl rubber, poly-(iso-butylene-altogether-p-methylstyrene), halogenation poly-(iso-butylene-be total to-p-methylstyrene), conventional rubber, natural rubber, polybutadiene rubber, polyisoprene rubber; styrene-butadiene rubber(SBR); styrene isoprene butadiene rubber (SIBR); isoprene-butadiene rubber; high-cis polybutadiene; ethylene-propylene rubber(EPR); ethylene-propylene-elastoprene; paracril; brominated butyl rubber; chlorinated butyl rubber; star-branched polyisobutene rubber and composition thereof.

[0014] in further embodiment, and combine with any above-mentioned disclosed aspect or embodiment, clay can be to be selected from following group exfoliated clays: exfoliate natural or synthetic montmorillonite, nontronite, beidellite, volkonskoite, LAPONITE, hectorite, saponite, sauconite, magadiite (magadite), fibrous morphology crystals, lucianite, vermiculite, halloysite, aluminate oxide compound, hydrotalcite and composition thereof.

[0015] in another embodiment still, and combine with any above-mentioned disclosed aspect or embodiment, elastic composition or air shield can further comprise the filler that is selected from down group: lime carbonate, mica, silica, silicate, talcum, titanium dioxide, starch, wood chip, carbon black and composition thereof.

[0016] these and other target, feature and advantage will become obvious with reference to following detailed description, preferred embodiment, embodiment and appended claim.

Detailed description of the Invention

[0017] described various specific embodiments, modification and embodiment at this, comprised that exemplary embodiment and being used to understands the definition of the object of the invention of requirement.Though following detailed description has provided concrete preferred embodiment, those skilled in the art only are exemplary when understanding these embodiments, and the present invention can otherwise implement.In order to determine infringement, scope of the present invention is one or more with reference to claims, comprise being equivalent to described those coordinator, and key element or restriction.It is one or more that the quoting of any " invention " can refer to, but the invention that claim limited that needn't be whole.

[0018] term " phr " refers to the umber of per 100 parts of rubber, and is the general standard of measurement in this area, and wherein the component of composition is measured with respect to the total amount of all elastomericss (rubber) component.No matter in given prescription, have one, two, three or multiple different rubber components, be defined as 100phr for the total phr or the umber of all rubber components.All other nonrubber components are asked ratio to 100 parts of rubber, and be expressed as phr.

[0019] term used herein " elastomerics " refers to any polymkeric substance consistent with ASTM D1566 (it is hereby incorporated by) definition or the combination of polymkeric substance.Term used herein " elastomerics " can use interchangeably with term " rubber ".

[0020] elastic composition of the present invention can comprise various elastomericss, hydrocarbon polymer additives (" HPA "), clay and filler.In one embodiment, various elastomericss are present in the elastic composition separately or with each other some combinations with 100phr usually, and HPA (one or more) exists to 50phr with 5.

[0021] in one embodiment, this elastic composition is used for tire or tyre assembly such as tire flap.In model tire flap mixing material, this elastic composition can comprise: the elastomerics (one or more) of 100phr; 5 to 50phr HPA (one or more); Randomly, about 50 to about 90phr filler, for example, carbon black and/or silicon-dioxide; Randomly, about 4 to about 15phr clay (one or more); Randomly, about 0.5 to 5phr ZnO; Randomly, about 1 to about 5phr stearic acid; Randomly, about 1 to 5phr promotor; Randomly, about 0.25 to 1.50phr sulphur; Randomly, other processing aid of about 5phr.

[0022] in some embodiments, HPA (one or more) can be used outside other processing aid and oils, or in other embodiments as the surrogate of other processing aid and oils.In preferred embodiments, this elastic composition is substantially free of perfume oil.Be substantially free of perfume oil and be defined as to refer to and perfume oil do not had a mind to add this elastic composition, or, in other words, if exist, this elastic composition comprises the perfume oil less than 0.5phr, or is more preferably less than the perfume oil of 0.25phr, or most preferably less than the perfume oil of 0.1phr.Perfume oil is to comprise the list of 35wt% at least-and many-the encircle compound of component.Usually, perfume oil comprises undersaturated many ring components.

[0023] in some embodiments, elastic composition can comprise naphthenic oil.In other preferred embodiment, elastic composition is substantially free of naphthenic oil.Be substantially free of naphthenic oil and be defined as to refer to and naphthenic oil do not had a mind to add elastic composition, or, in other words, if exist, this elastic composition comprises the naphthenic oil less than 0.5phr, or is more preferably less than the naphthenic oil of 0.25phr, or most preferably less than the naphthenic oil of 0.1phr.Usually, cycloalkanes oils has as the second-order transition temperature (Tg) of about 0.85 viscosity gravity constant as described in the ASTM D2501, pact-60 ℃ with as about 90 nominal aniline point as described in the ASTM D611.

Elastomerics

[0024] elastic composition comprises at least a elastomerics.The general elastomerics that can be included in the elastic composition is based on C ₄To C ₇The rubber of monoolefine, as isoprene-isobutylene rubber (isoprene-isobutene rubber, " IIR "), branching (" star-branching ") isoprene-isobutylene rubber, star-branched polyisobutene rubber, brominated butyl rubber (" BIIR "), chlorinated butyl rubber (" CIIR "), the random copolymers of iso-butylene and p-methylstyrene (poly-(iso-butylene-altogether-p-methylstyrene)), halogenation poly-(iso-butylene-be total to-p-methylstyrene) (" BIMSM "), polybutadiene rubber (" BR "), high-cis polybutadiene, polyisoprene rubber, isoprene-butadiene rubber (" IBR "), styrene isoprene butadiene rubber (SIBR) (" SIBR "); styrene-butadiene rubber(SBR) (" SBR "), solution-styrene-butadiene rubber(SBR) (" sSBR "), emulsion-styrene-butadiene rubber(SBR), paracril, ethylene-propylene rubber(EPR) (" EP "), ethylene-propylene-elastoprene (" EPDM "), synthetic polyisoprenes, conventional rubber, natural rubber, these elastomeric any halogenated form and composition thereof.Preferred elastomerics comprises based on the elastomerics of iso-butylene such as IIR, halogenation IIR and halogenation poly-(iso-butylene-be total to-p-methylstyrene).Useful elasticity physical efficiency makes by any suitable method well known in the prior art, and the present invention is not prepared the restriction of elastomeric method in this article.

[0025] in some embodiments, elastic composition comprises two or more elastic blends.Elastomeric blend can be reactor blend and/or fusion mixture.Independent elastomeric component can be different amount exist, total elastomer content is expressed as 100phr in the elastic composition in prescription.

[0026] useful elastomerics comprises homopolymer or the multipolymer based on iso-butylene.Refer to based on the elastomerics of iso-butylene and to comprise that 70mol% is from the elastomerics or the polymkeric substance of the repeating unit of iso-butylene at least.These polymkeric substance can be described to C ₄To C ₇The random copolymers of isomonoolefin derived units such as iso-butylene derived units and at least a other polymerizable unit.Elastomerics based on iso-butylene can be halogenation or not halogenated.

[0027] elastomerics can also be butyl-type rubber or branched butyl-type rubber, comprises these elastomeric halogenated form.Useful elastomerics is the homopolymer and the multipolymer of unsaturated isoprene-isobutylene rubber such as alkene, isoolefine and polyene hydrocarbon.The limiting examples of the unsaturated elastic body that other is useful is poly-(iso-butylene-be total to-isoprene), polyisoprene, polyhutadiene, polyisobutene, poly-(vinylbenzene-be total to-divinyl), natural rubber, star-branched butyl rubber and composition thereof.

[0028] this elastomerics can be halogenation or not halogenated.Preferred halogenated elastomer is optional from following group: halogenated butyl rubber, brominated butyl rubber, chlorobutyl rubber, halogenation branching (" star-branching ") isoprene-isobutylene rubber, and the halogenation random copolymers of iso-butylene and p-methylstyrene.Halogenation can be carried out by any way, and the present invention can't help halogenated method in this article and limits.

[0029] in one embodiment, elastomerics can be branching or " star-branching " isoprene-isobutylene rubber (" SBB ").SBB generally is halogenation or not halogenated isoprene-isobutylene rubber, and the halogenation or the composition of halogenation polydiene or segmented copolymer not.In one embodiment, SBB or halogenation-SBB are the compositions of the multipolymer of butyl or halogenated butyl rubber and polydiene and partial hydrogenation polydiene, wherein polydiene is selected from vinylbenzene, polyhutadiene, polyisoprene, poly-(1,3-pentadiene), natural rubber, styrene-butadiene rubber(SBR), ethylene-propylene elastoprene (" EPDM "), ethylene-propylene rubber(EPR) (" EP "), styrene-butadiene-styrene and styrene isoprene styrene block copolymer (SIS).These polydiene exist greater than 0.3wt% in one embodiment with based on monomer wt%, or in another embodiment in 0.3 to 3wt% scope or in 0.4 to 2.7wt% scope.

[0030] elastomerics can be to comprise C ₄To C ₇Isomonoolefin such as iso-butylene and ring-alkylated styrenes comonomer are as the random copolymers of the p-methylstyrene of the para-isomeride that comprises at least 80% or at least 90% weight meter.In one embodiment, this polymkeric substance can be ethene or C ₃To C ₆Alpha-olefin and the ring-alkylated styrenes comonomer as the random elastomeric precursor copolymer of the p-methylstyrene of the para-isomeride that comprises at least 80% or at least 90% weight meter.

[0031] this multipolymer can be chosen the interpretation that comprises functionalization wantonly, wherein is present in styrene monomer unitary at least one or a plurality of alkyl substituent and comprises halogen or some other functional groups.In one embodiment, the vinylbenzene until the para-orientation of 60mol% that is present in the unregulated polymer structure can be functionalized.In another embodiment, the amount of functionalized p-methylstyrene arrives in the scope of 5mol% 0.1, or arrives in the scope of 3mol% 0.2.Functional group can be that halogen maybe can pass through with other group such as carboxylic-acid; Carboxylate salt; Carboxyl ester, acid amides and imide; Hydroxyl; Alkoxide; Phenates; Thiolate; Thioether; Xanthate; Prussiate; Cyanate; Amino and composition thereof nucleophilic substitution benzylic type (benzylic) halogen and some other functional groups of bonded.These functionalized isomonoolefin copolymers, their preparation method, functionizing method and sulfuration more specifically are disclosed in U.S. Patent No. 5,162, in 445, it are hereby incorporated by.

[0032] in further embodiment, elastomerics is iso-butylene and comprises 0.5 random copolymers to the p-methylstyrene of 20mol% p-methylstyrene, wherein the methyl substituents that is present on the benzyl rings of 60mol% comprises bromine or chlorine atom at the most, and acid or ester functional modification.

[0033] in certain embodiments, random copolymers has basically to form uniformly and distributes, make the polymkeric substance of 95wt% at least have polymkeric substance on average to ring-alkylated styrenes content 10% in to ring-alkylated styrenes content.Exemplary polymer features is less than 5 or less than 2.5 narrow molecular weight distributions (Mw/Mn), 200,000 up to 2,000, exemplary viscosity-average molecular weight in 000 scope and during by gel permeation chromatography 25, exemplary number-average molecular weight in 000 to 750,000 scope.

[0034] elastomerics can be poly-(iso-butylene-be total to-p-methylstyrene) (" BIMSM ") of bromination.The BIMSM polymkeric substance comprises 0.1 to 5% mole brooethyl vinylbenzene with respect to monomer derived units total amount in the multipolymer usually.In one embodiment, the amount of brooethyl arrives in the scope of 3.0mol% 0.2, or 0.3 in the scope of 2.8mol%, or 0.4 in the scope of 2.5mol%, or 0.3 in the scope of 2.0mol%, wherein desirable scope can be arbitrary combination of arbitrary upper limit and arbitrary lower limit.Express with another kind of method, exemplary multipolymer can comprise based on polymer weight 0.2 to the bromine of 10wt%, or 0.4 to the 6wt% bromine, or 0.6 to 5.6wt%, in another embodiment, they are substantially free of ring halogen or the halogen in polymer backbone chains.In one embodiment, unregulated polymer is C ₄To C ₇Isoolefine derived units (or isomonoolefin), p-methylstyrene derived units and to the multipolymer of (monochloromethyl vinylbenzene) derived units, wherein (monochloromethyl vinylbenzene) unit is present in the polymkeric substance with 0.4 to 3.0mol% scope based on the p-methylstyrene total amount, and wherein the p-methylstyrene derived units to exist based on 3 to 15wt% scope of total polymer or 4 to 10wt% scope.In a preferred embodiment, be to (brooethyl vinylbenzene) to (monochloromethyl vinylbenzene).

[0035] the commercial specific examples of useful halogenated isobutylene-p-methylstyrene rubber comprises EXXPRO ^TMElastomerics, can be from Exxon Mobil Chemical Company, Houston, TX obtains, it has mooney viscosity in 30 to 50 scopes, and (ML1+8 is under 125 ℃, ASTMD1646), at 4 p-methylstyrene content and 0.7 bromine contents that arrive in the 2.2wt% scope that arrive in the 8.5wt% scope, with respect to halogenated isobutylene-p-methylstyrene rubber.

[0036] in further embodiment, elastomerics can be the rubber based on non-iso-butylene of at least a routine type that is used for the rubber for tire compounding, and is called " conventional rubber " in this article.Conventional rubber can be any rubber that high strength and good wearing and tearing and low hysteresis and high resilience are provided usually.

[0037] example of conventional rubber comprises natural rubber (" NR "), polyisoprene rubber (" IR "), poly-(vinylbenzene-be total to-divinyl) rubber (" SBR "), polybutadiene rubber (" BR "), poly-(isoprene-be total to-divinyl) rubber (" IBR "), styrene isoprene butadiene rubber (SIBR) (" SIBR ") and composition thereof.Ethylene-propylene rubber(EPR) (" EP ") and ethylene-propylene-elastoprene (" EPDM ") and composition thereof also are known as conventional rubber.

[0038] in one embodiment, this elastomerics can comprise polybutadiene rubber (" BR ").(ML1+4 ASTMD1646) can be in 35 to 70 scope, or 40 to about 65, or in another embodiment in 45 to 60 scope at the mooney viscosity of 100 ℃ of polybutadiene rubbers of measuring down.Another kind of useful conventional rubber is high-cis polybutadiene (" cis-BR ").For " cis-polybutadiene " or " high-cis polybutadiene ", it refers to adopts 1, the 4-cis-polybutadiene, and wherein the amount of cis component is at least 90%.

[0039] elastomerics can be polyisoprene (IR) rubber.Can be in 35 to 70 scope at the mooney viscosity (ML1+4, ASTM D1646) of 100 ℃ of polyisoprene rubbers of measuring down, or 40 to about 65, or in another embodiment in 45 to 60 scope.

[0040] this elastic composition can comprise the rubber of ethene and propylene derived unit such as EP and EPDM as suitable less important elastomerics.The example of suitable comonomer is an ethylidene norbornene, 1 in preparation EPDM, 4-hexadiene, Dicyclopentadiene (DCPD), and other.In one embodiment, elastic composition can comprise the ethylene/alpha-olefin/diene terpolymer.Alpha-olefin can be selected from C ₃To C ₂₀Alpha-olefin, propylene, butylene and octene are preferred, and propylene most preferably.Diene component can be selected from C ₄To C ₂₀Diene.

[0041] in one embodiment, one or more elastomericss can be natural rubbers.The desirable embodiment of natural rubber can be selected from technical regulation rubber (" TSR ") as Malaysian rubber, and it includes but not limited to SMR CV, SMR 5, SMR 10, SMR 20, SMR 50 and composition thereof.Preferred natural rubber has the mooney viscosity (ML1+4, ASTM D1646) in 30 to 120 scopes under 100 ℃, or 40 to 80 scope.

[0042] elastomerics that can the present invention is useful and various other rubber or plastics, particularly thermoplastic resin are as nylon or for example polypropylene or the mixing of polyacrylic multipolymer of polyolefine.These compositions be useful in other application of air shield such as the high air or oxygen maintenance of air bag, tube, tire flap, casing air (as in air cushion shock absorber), barrier film and needs.

[0043] in preferred embodiments, elastomerics is selected from poly-(iso-butylene-be total to-ring-alkylated styrenes), preferred poly-(iso-butylene-be total to-p-methylstyrene), halogenation poly-(iso-butylene-be total to-ring-alkylated styrenes), preferred halogenation poly-(iso-butylene-be total to-p-methylstyrene), star-branched butyl rubber, halogenated star branched butyl rubber, isoprene-isobutylene rubber, halogenated butyl rubber and composition thereof.In a further preferred embodiment, elastomerics comprises brominated butyl rubber or chlorinated butyl rubber.

Hydrocarbon polymer additives

[0044] elastic composition can further comprise hydrocarbon polymer additives (" HPA ").HPA is usually derived from petroleum streams, and can be hydrogenation or hydrogenated resin not.Useful HPA including, but not limited to aliphatics HPA, the aliphatics/anine of aliphatics HPA, fragrant modification, encircle resin, hydrogenation more and encircle resin, many cyclophanes of hydrogenation resinoid more, wherein most phenyl ring be converted into hydrogenated aromatic resin, rosin, rosin ester, wood rosin, wood rosin ester, starex, starex ester, polyterpene, fragrant modification polyterpene, terpenes phenoplast and the combination thereof of cyclohexane ring.

[0045] can be with HPA as the elastomer material.Depend on how compounding, can realize the rubber property optimization of rubber and tyre last, traction and resistance to abrasion HPA.For example, usually naphthenic oil is added in the tire flap compounding preparation to guarantee mixing material sufficient processing quality in tire production factory.Yet the naphthenic oil tool has adverse influence owing to increasing the liner perviousness.Use HPA to replace naphthenic oil can allow to keep mixing material processing characteristics such as mooney viscosity, and improve the liner pressuretightness simultaneously.Replace cycloalkanes treated oil tolerable to keep liner mixing material factory process quality also therefore for example can improve other character with HPA, but be not limited to fatigue resistance, persistence and/or pressuretightness.

[0046] character of HPA (molecular weight, molecular weight distribution, second-order transition temperature, branching etc.) can be controlled from its deutero-raw material by changing HPA.HPA can be produced by plurality of raw materials; For example in some embodiments, the main ingredient of raw material can be a 1,3-pentadiene, and cyclopentadiene can be a main ingredient in other embodiments, and in further embodiment, the overhead product that comprises Vinyl toluene and indenes can be a main ingredient.

[0047] character of HPA also is subjected to the microtexture of resin, and promptly the type of monomer component and amount influence.Monomer layout in the resin chain is at random, causes further complicacy in the micmstructure of polymer.For example, some resins can comprise the aliphatic hydrocarbon component, and it has by the 1,3-pentadiene that comprises variable number, isoprene, monoolefine and C that can not the polymeric chain hydride compounds ₄-C ₆The hydrocarbon chain that cut forms.Such HPA can be based on amylene, butane, isoprene, 1,3-pentadiene, and comprises cyclopentadiene and the Dicyclopentadiene (DCPD) that reduces quantity usually.HPA also can comprise the aromatic hydrocarbons structure with the polymer chain that is formed by fragrant unit such as vinylbenzene, dimethylbenzene, alpha-methyl styrene, Vinyl toluene and indenes.Other HPA can mainly comprise cyclopentadiene and/or Dicyclopentadiene (DCPD).

[0048] HPA can comprise " aliphatics " and/or " aromatic series " component.Preferred aliphatic olefin is C ₄To C ₂₀, preferred C ₄To C ₇, more preferably C ₅To C ₆Line style, branching or alicyclic olefin or non-conjugated diene hydrocarbon.Preferred aromatic olefin comprises one or more of vinylbenzene, indenes, styrene derivatives and indene derivative.Particularly preferred aromatic olefin comprises vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, indenes and methyl indenes and Vinyl toluene (tolunes).In preferred embodiments, HPA comprises the monomer derived from 1,3-pentadiene, isoprene, amylene, ring compound, vinylbenzene, indenes or its combination.

[0049] 1,3-pentadiene C normally ₅The cutting cut or the synthetic mixture of diolefine, it includes but not limited to cis-1,3-pentadiene, anti-form-1,3-pentadiene and mixing 1,3-pentadiene.Usually, 1,3-pentadiene does not comprise the C of branching ₅Diolefine such as isoprene.

[0050] ring compound C normally ₅And C ₆The cutting cut or the synthetic mixture of cyclic olefin, diolefine and dipolymer thus.Ring compound includes, but are not limited to cyclopentenes, cyclopentadiene (" CPD "), Dicyclopentadiene (DCPD) (" DCPD "), tetrahydrobenzene, 1 and 1.The definition of term Dicyclopentadiene (DCPD) comprises the DCPD of interior and outer form.Preferred ring compound is a cyclopentadiene.Ring compound can be substituted; The preferred ring compound that replaces comprises uses C ₁To C ₄₀Line style, branching or cyclic alkyl, preferred one or more methyl substituted CPD and DCPD.Methyl cyclopentadiene is preferred substituted-cyclopentadienyl.

[0051] HPA can comprise one or more styrenic component such as vinylbenzene, styrene derivatives and substituted phenylethylene.Usually, styrenic component does not comprise fused rings such as indenes.

[0052] HPA can comprise one or more indenes class components such as indenes and indene derivative.

[0053] in some embodiments, styrenic component can tend to reduce the softening temperature of HPA.Other aromatics (particularly indene compounds) may tend to improve the softening temperature of HPA.In other embodiments, HPA can comprise that tending to have broaden effect and tending to of the molecular weight distribution of making improves the CPD and the DCPD of the softening temperature of HPA.

[0054] HPA can produce by the common known method in field of producing hydrocarbon resin.For example, in some embodiments, HPA is by thermopolymerization production, and in other embodiments, HPA can produce by catalyzed polymerization.Polymerization and stripping condition can be adjusted according to the character of the charging that obtains required resin.

[0055] in one embodiment, HPA can pass through the incompatible preparation of hot polymerization.For example, resin can by the charging that comprises cyclopentadiene in benzene or toluene solvant in the down thermopolymerization 2.0 to 4.0 hours of the pressure (1.4MPa) of 220 ℃ to 280 ℃ and about 14 crust, and adjusting condition is with the molecular weight and the softening temperature of control resin.Charging can further comprise the dimer and the codimers of alkyl cyclopentadiene, cyclopentadiene and methyl cyclopentadiene, and other non-annularity diene is as 1,3-piperylene and isoprene.But unsaturated monomer such as vinyl aromatic compound such as vinylbenzene, alpha-methyl styrene, indenes and the Vinyl toluene that can also have other copolymerization.

[0056] in another embodiment, HPA can catalyzed polymerization.The preferred method of producing resin be with feedstream in polymerization reactor with Knut Fridell-Kerafyrm thatch or lewis acid catalyst 0 ℃ and 200 ℃ of scopes, preferably combination under the temperature in the scope of 20 ℃ and 80 ℃.Knut Fridell-Kerafyrm thatch polymerization is usually by using known catalyzer in polymer solvent, and removes by washing and distillation and to desolvate and catalyzer is finished.Polymerization technique can be intermittence or continuous mode, and successive polymerization can be a single-stage or multistage.Spendable friedel-crafts catalysts is including, but not limited to Lewis acid boron trifluoride (BF for example ₃), the title complex of boron trifluoride, aluminum chloride (AlCl ₃) or aluminum alkyl halide muriate particularly.In one embodiment, the lewis acidic amount that can be used in the catalyzer is to arrive the scope of 3.0wt%, preferred 0.5 to 1.0wt% based on 0.3 of charging blend weight.Aluminum trichloride catalyst preferably uses as powder.

[0057] in preferred embodiments, resin can be hydrogenated.Any currently known methods that is used for the catalytic hydrogenation resin can be used for hydrogenated resin.The hydrogenation of hydrocarbon resin can be by continuous processing intermittently or more generally via carrying out based on the method for fusion or solution.The catalyzer that is used for hydrogenation HPA is the monometallic and the bimetallic catalyst system of general load.Spendable catalyzer can comprise VIII family metal for example nickel, palladium, ruthenium, rhodium, cobalt and platinum, and VI family metal is tungsten, chromium and molybdenum for example, and VII family metal is rhenium, manganese and copper for example, and other catalyzer can be based on the 9th, 10 or 11 family's elements.These metals can be separately or with being used in combination of two or more metals, with metallic forms or with activated form and can directly use or load on solid carrier such as aluminum oxide or silica-alumina.Solid support material generally comprises the inorganic refractory oxides of porous such as silicon-dioxide, magnesium oxide, silica-magnesia, zirconium white, silicon-dioxide-zirconium white, titaniferous silica-titania, aluminum oxide, silicon-dioxide-manosil AS aluminium etc.Preferably, carrier is substantially free of the crystalline molecular screen material.Also can imagine above-mentioned hopcalite, particularly in the time preparing as far as possible equably.Preferred carrier comprises aluminum oxide, silicon-dioxide, carbon, MgO, TiO ₂, ZrO ₂, FeO ₃Or its mixture.

[0058] HPA can be a polarity or nonpolar." nonpolar " expression HPA is substantially free of the monomer with polar group.Preferably do not have polar group, yet if exist, preferably they preferably are no more than 2wt% to be no more than 5wt%, even exist more preferably no more than 0.5wt%.

[0059] example of commercially available HPA comprises: OPPERRA ^TM373,394,103, all can obtain from ExxonMobil Chemical Company.

[0060] in one embodiment, HPA has the melt viscosity 160 ℃ of following 300 to 800 centipoise (cPs) scopes, or preferably 160 ℃ of following melt viscosities of 350 to 650cPs.In preferred embodiments, the melt viscosity of HPA arrives in the 615cPs scope 375 under 160 ℃, or arrives in the 600cPs scope 475 under 160 ℃.Melt viscosity can record by ASTM D6267 by the Brookfield viscometer with the rotating shaft of " J " type.

[0061] in other embodiments, HPA has greater than about 600g/mol or greater than the weight-average molecular weight (Mw) of about 1000g/mol.In at least one embodiment, HPA has 1650 to 1950g/mol, or the weight-average molecular weight (Mw) of 1700 to 1900g/mol scope.Preferably HPA has 1725 weight-average molecular weight to the 1890g/mol scope.HPA can have 450 in the 700g/mol scope, or 500 to 675g/mol, or preferably in 520 number-average molecular weights (Mn) in the 650g/mol scope.HPA can have 5850 to the 8150g/mol scope, or more preferably at the 6000 z-average molecular weights (Mz) to the 8000g/mol scope.Mw, Mn and Mz can pass through gel permeation chromatography (GPC) and measure.

[0062] in one embodiment, HPA have 4 or littler polydispersity index (" PDI ", PDI=Mw/Mn).In preferred embodiments, HPA has the PDI in 2.6 to 3.1 scopes.

[0063] in some embodiments, HPA has at about-30 ℃ of second-order transition temperatures (Tg) to about 100 ℃ of scopes, or about 0 ℃ to about 80 ℃, or about 40 ℃ to about 60 ℃, or about 45 ℃ to about 55 ℃, or preferably arrive in about 53 ℃ of scopes at about 48 ℃.Dsc (DSC) can be used for measuring the Tg of HPA.The following description of process of dsc (" DSC ").Polymkeric substance is being extruded in the squeezer of heating under about 200 ℃ to about 230 ℃, and the polymer sheet that obtains is being suspended under envrionment conditions in the air with cooling.About polymer sheet of 6 to 10mg is taken out with punch die.These 6 to 10 milligrams of samples were at room temperature annealed about 80 to 100 hours.In this section time end, sample is put into differential scanning calorimeter (" DSC ") (PerkinElmer Pyris One Thermal Analysis System) and be cooled to-50 ℃ to-70 ℃ approximately approximately.Sample is reached about 200 ℃ outlet temperature with 10 ℃/min heating.With sample remain on 200 ℃ following 5 minutes and carry out second cooling-heating cycle.Write down the round-robin situation twice.Thermal output is recorded as area under the sample melted peak, and this generally occurs between about 0 ℃ and about 200 ℃.Total absorption of sample or release energy and be Δ H in test process is expressed as joule every gram polymkeric substance.Fusing point is recorded as the temperature that absorbs with respect to the baseline maximum heat in the sample melting range.

[0064] in one or more embodiments, HPA has at least 400 Mn, at least 500 Mw, and at least 700 Z-average molecular weight (Mz) and at least 1.5 polymolecularity (Mw/Mn), wherein Mn, Mw and Mz are by gel permeation chromatography.Similarly, resin has the Mn until 2000, the Mw until 3500, the Mz until 15,000 and until 4 polymolecularity (Mw/Mn).

[0065] in one embodiment, resin has the ring and ball softening point of measuring by ASTM E28-99 in 10 ℃ to 140 ℃ scopes, preferred 80 ℃ to 120 ℃.In another embodiment, resin has 4000 or weight-average molecular weight still less (Mw), preferably in 500 to 4000 scope, preferably in 500 to 2500 scope.In another embodiment, resin has 3 or Mw/Mn still less, preferably in 1 to 2.4 scope, or in 1 to 2 scope.

[0066] HPA can comprise one or more of 1,3-pentadiene, ring compound, isoprene, amylene, indenes class component and/or styrenic component of different quantities.

[0067] in one embodiment, HPA comprises 40 to 90wt% 1,3-pentadiene, or 50 to 90wt%, or more preferably 60 arrive 90wt%.In another embodiment, HPA comprises 70 to 90wt% 1,3-pentadiene.

[0068] in some embodiments, HPA is substantially free of isoprene.In other embodiments, HPA comprises the isoprene until 5wt%, or more preferably until the 10wt% isoprene.In another embodiment, HPA comprises the isoprene until 15wt%.

[0069] in some embodiments, HPA is substantially free of amylene.In other embodiments, HPA comprises the amylene until 10wt%, or more until the 25wt% amylene, or until the 30wt% amylene.In another embodiment, HPA comprises the amylene until 40wt%.

[0070] in some embodiments, aromatic olefin generally is present among the HPA to 45wt% with 5, or more preferably 5 arrives 30wt%.In preferred embodiments, HPA comprises 10 to the 20wt% aromatic olefin.

[0071] in one embodiment, HPA comprises until the styrenic component of 60wt% or until the styrenic component of 50wt%.In one embodiment, HPA comprises 5 to 30wt% styrenic component, or 5 to 20wt% styrenic component.In preferred embodiments, HPA comprises 10 to 15wt% styrenic component.

[0072] in another embodiment, HPA can comprise the indenes class component until 15wt%, or until 10wt% indenes class component.Indenes class component comprises the derivative of indenes and indenes.In one embodiment, HPA comprises the indenes class component until 5wt%.In another embodiment, HPA is substantially free of indenes class component.

[0073] in one embodiment, HPA can comprise until the ring compound of 60wt% or until the ring compound of 50wt%.In some embodiments, HPA comprises ring compound with about 0.1wt% to the consumption of about 50wt% scope, or about 0.5wt% is to the ring compound of about 30wt%, or comprises that about 1.0wt% arrives the ring compound of about 20wt%.In other embodiments, HPA comprises the ring compound of about 5wt% to about 15wt%.

[0074] in other preferred embodiment, HPA can comprise the ring compound greater than 75wt%, or greater than 80wt%, or greater than the 90wt% ring compound.In some embodiments, HPA can be made up of ring compound basically.

[0075] in another embodiment, HPA comprises Dicyclopentadiene (DCPD) (" DCPD ") and methyl substituted DCPD isomer, and its hot polymerization is merged hydrogenation then to remove any unsaturated double-bond.HPA have have some carbon-to-carbon side chains closely and inflexible " scalariform " structure.HPA has about 120 ℃ softening temperature and about 70 ℃ Tg.

[0076] in particularly preferred embodiments, HPA comprises the Dicyclopentadiene (DCPD) of Dicyclopentadiene (DCPD) or replacement.Preferred HPA has about 410 Mn, about 630 Mw and about 1020 Mz.This resin have by ASTM E28-99 measure at about 115 softening temperatures to about 130 ℃ of scopes.

[0077] in one embodiment, HPA can comprise the 1,3-pentadiene of 50-90wt%, the isoprene of 0-5wt%, amylene, 0-5wt% ring compound, the styrenic component of 0-10wt% and the indenes class component of 0-10wt% of 10-30wt%.This resin can have the melt viscosity from 375cPs to 515cPs under 160 ℃, the Mn of 700-900g/mol, the Mw of 1400-1800g/mol, the Tg of the Mz of 3000-5000g/mol and 45 ℃ to 50 ℃.

[0078] in another embodiment, HPA can comprise the 1,3-pentadiene of 60-90wt%, the isoprene of 0-5wt%, amylene, 5-15wt% ring compound, the styrenic component of 5-20wt% and the indenes class component of 0-5wt% of 0-10wt%.This resin can have the melt viscosity from 375cPs to 615cPs under 160 ℃, the Mn of 520-650g/mol, the Mw of 1725-1890g/mol, the Tg of the Mz of 6000-8200g/mol and 48 ℃ to 53 ℃.

[0079] in another embodiment, HPA can comprise Dicyclopentadiene (DCPD) and methyl substituted Dicyclopentadiene (DCPD).Resin can have 110 to 150 ℃ the softening temperature of measuring by ASTM E28-99, or in about 115 to 130 ℃ scope.Resin can have the Tg in 60 to 80 ℃ of scopes, or in 65 to 75 ℃ of scopes, or in 67 to 73 ℃ of scopes.Resin can have 350 to the interior Mn of 450g/mol scope, or arrives in the 430g/mol scope 370, or arrives in the 420g/mol scope 390, or arrives in the 415g/mol scope 400.This resin can have 500 to the Mw of 700g/mol, or 550 in the 675g/mol scope, or 600 to the 650g/mol scope.This resin can have 950 to the interior Mz of 1100g/mol scope, or arrives in the 1050g/mol scope 980, or arrives in the 1030g/mol scope 1000.

[0080] in further embodiment, HPA can form as the Dicyclopentadiene (DCPD) of Dicyclopentadiene (DCPD) and replacement basically by ring compound.Resin can have the softening temperature of measuring by ASTM E28-99 in about 115 to 130 ℃ of scopes, about 70 ℃ Tg, the Mn of about 410g/mol, the Mw of about 630g/mol and the Mz of about 1020g/mol.

Nano composite material

[0081] nano composite material is to comprise at least one dimension at the polymeric system of the inorganic particle of nanometer range.The inorganic particle that is used for the universal class of nano composite material is a phyllosilicate, from the inorganic substance of common classification what is called " nanoclay " or " clay ".Owing to the common enhancing of various elastic composition hollow gas shield quality when having nano composite material, need comprise the elastic composition of nano composite material, this nano composite material comprises elastomerics and clay.

[0082] inorganic particle (for example clay) can be used as the sheet shield that oxygen sees through the elastic composition transmission.Yet, inorganic particle need be disperseed to spread all over elastic composition fully for effectively.This may be difficult, because require the dispersion of polarity clay in common non-polar rubber usually.

[0083] ideally, intercalation should occur in the nano composite material, wherein in the space or passage between the polymkeric substance insertion surface of clay.At last, have that almost completely to peel off be desirable, wherein the clay platelet of polymkeric substance with each nanoscale fully disperseed or intercalation.

[0084] the suitable inorganic particle that is used for nano composite material can comprise the inorganic clay material of swellable, as natural or synthetic phyllosilicate, particularly smectic type (smectic) clay if you would take off stone, nontronite, beidellite, volkonskoite, LAPONITE, hectorite, saponite, sauconite, magadiite, fibrous morphology crystals, lucianite etc., and vermiculite, halloysite, aluminate oxide compound, hydrotalcite etc.These laminated claies generally include comprise a plurality of with

Or the thickness that is closely linked of littler interlamellar spacing

The particle of silicate thin slice, and comprise exchangeable cation such as the Na that is present in interlayer surface ⁺, Ca ^{+ 2}, K ⁺Or Mg ^{+ 2}

[0085] in some embodiments, clay can mix with organic liquid to form clay dispersion.Clay can be inorganic clay or organo-clay; Organic liquid can be mixable or immiscible in water.In certain embodiments, this dispersion can have 0.1 to the interior clay content of 5.0wt% scope, or arrives in the scope of 3.0wt% 0.1.

[0086] laminated clay can also be by handling with the organic molecule that generally is called swelling or scale off agent or additive intercalation and peeling off.The positively charged ion that swelling/exfoliant can exist with the interlayer surface at laminated clay carries out ion exchange reaction.For example, the clay of intercalation/peel off can produce by the ion exchange reaction based on solution, and wherein ion exchange reaction replaces being present in the sodium ion on sodium smectite clay surface as the alkyl or aryl ammonium compound with organic molecule (swelling/exfoliant).

[0087] suitable exfoliant comprises cats product as ammonium ion, alkylamine or alkyl phosphate ion (primary, secondary, uncle and Ji), the phosphorus or the sulfonium derivative of aliphatic, aromatic series or aryl aliphatic amine, phosphine and sulfide.Desirable amine compound (or corresponding ammonium ion) is to have structure R ¹R ²R ³Those of N, wherein R ¹, R ²And R ³Be C in one embodiment ₁To C ₃₀Alkyl or be C in another embodiment ₂To C ₃₀Alkyl or alkene, it can be identical or different.In one embodiment, exfoliant is so-called long chain tertiary amine, wherein R at least ¹Be C ₁₄To C ₂₀Alkyl or alkene.

[0088] exfoliant can also be diamine compound (or corresponding ammonium or two ammonium ions), as Diaminoalkane, N-alkyl-Diaminoalkane, N, N-dialkyl group-Diaminoalkyl, N, N, N '-trialkyl-Diaminoalkane, N, N, N ', N '-tetraalkyl-Diaminoalkane etc.Desirable diamines can have structure R ⁴R ⁵N-R ⁶-NR ⁷R ⁸, R wherein ⁴, R ⁵, R ⁶, R ⁷And R ⁸Be identical or different C ₁To C ₃₀Alkyl, or C ₂To C ₃₀Alkyl or alkene.When requiring the long-chain diamines, at least one of N-alkyl or N-alkene has 8 to 30 carbon atoms, preferred 14 to 20 carbon atoms.Concrete nonrestrictive illustrative examples comprises N-cocoyl-1,3-diaminopropanes, N-oil base-1,3-diaminopropanes, N-tallow base-1,3-diaminopropanes and N, N, N '-trimethylammonium-N '-tallow base-1,3-diaminopropanes.

[0089] another kind of exfoliant comprises those that can be covalently bound to interlayer surface.These comprise structure-Si (R ¹⁵) ₂R ¹⁶Polysilane, R wherein ¹⁵Occur being identical or different and being selected from alkyl, alkoxyl group or TMOS and R at every turn ¹⁶Be the organic group compatible with the matrix polymer of matrix material.

[0090] other suitable exfoliant comprises protonated amino acid and salt such as 12 amino dodecanoic acid, ε-Ji Neixianan and the materials similar that comprises 2-30 carbon atom.Suitable swelling agent and the method that is used for intercalation laminated clay silicate also are disclosed in US4, and in 472,538,4,810,734 and 4,889,885, all these documents are hereby incorporated by.

[0091] in preferred embodiments, exfoliant (one or more) can help the title complex of exfoliated clay with the halogen site reaction on the interpretation with formation.In one embodiment, this reagent comprises whole primary, second month in a season and tertiary amine and phosphine; Alkyl and aromatic yl sulfide and mercaptan; And their multifunctional form.Desirable reagent comprises: long chain tertiary amine such as N, N-dimethyl-octadecylamine, N, N-two (octadecyl)-methylamine, so-called di-H tallow base alkyl-methylamine etc. and amine-terminated polytetrahydrofuran; Long-chain mercaptan and thiosulfuric acid salt compound such as hexa-methylene Sulfothiorine.

[0092] in one embodiment, exfoliant can 0.1 exists to the scope of the scope of 20phr or 0.2 to 15phr, perhaps in another embodiment in 0.3 to 10phr scope.Exfoliant can be added composition in any stage; For example, this reagent can be added interpretation, then add clay, perhaps can add in the mixture of interpretation and clay; Perhaps in another embodiment, additive at first can be mixed with clay, then mix with interpretation.

[0093] in another embodiment, the pressuretightness of improvement realizes by the existence of at least a multifunctional vulcanizing agent.The example of multifunctional vulcanizing agent like this can be used formula Z--R ¹⁷--Z ' description, wherein R ¹⁷Be to replace or unsubstituted C ₁To C ₁₅Alkyl, C ₂To C ₁₅Alkenyl and C ₆To C ₁₂In the ring-type aromatic series part one; And Z and Z ' are identical or different, be thiosulfate anion group, sulfydryl, aldehyde radical, carboxyl, peroxidation group, alkenyl or can be at other similar group of intermolecular or intramolecular crosslinking, one or more chain links (strand) of polymkeric substance have active group such as unsaturated part.Multifunctional vulcanizing agent is if exist, can 0.1 to 8phr scope or be present in composition in 0.2 to 5phr scope in another embodiment.

[0094] elastic composition also can comprise anti-reversion agent (reversionresistors).The limiting examples of anti-reversion agent like this comprises two-thiosulfuric acid salt compound, as hexa-methylene two (Sulfothiorine).Other anti-reversion agent is known in the rubber compounding field, as hexa-methylene two (phenylacrolein).

[0095] since keep the clay platelet layer ion bonding force together minimizing and be introduced in interlayer play with greater than

Be preferably greater than

The result of molecule of effect of separating distance layer, handle intercalation or " the peeling off " that causes the laminated clay platelet with swelling agent.This separation makes that laminated clay silicate is easier and absorbs polymerisable monomer material and polymkeric substance at interlayer, and when intercalation thing and matrix polymer material shear-mixed the time layering of further promoting layer so that the homogeneous dispersion of the clay seam that peels off to be provided in polymeric matrix.

[0096] amount that is combined in clay in the elastic composition or exfoliated clay is enough to manifest the mechanical property of composition or the improvement of barrier property by forming nano composite material.The amount of clay in elastic composition usually in based on composition 0.5 of polymer content in the scope of 10wt%, or 1 in the scope of 8wt%, or in another embodiment in 1 to 5wt% scope.Umber with per 100 parts of rubber represents, scope that clay or the clay that peels off can 1 to 30phr or 2 to 20phr scope exist.

[0097] elastomerics-clay nanocomposites can adopt the whole bag of tricks well known in the prior art to form, as solution mixing, melting mixing or emulsion process.The U.S. Patent Application Publication 2007/015853 that for example is hereby incorporated by discloses a kind of method of the emulsion preparation clay-butyl rubber nanocomposites by rubber solutions and moisture clay dispersion system, and its medium clay soil can be an inorganic clay.Another embodiment as nano composite material processing, the U. S. application sequence number 11/183,361 that is hereby incorporated by discloses and has a kind ofly prepared spissated nano composite material and enriched material is mixed the method for preparing clay-butyl rubber nanocomposites with main rubber logistics by the slip-stream by rubber.

[0098] in one embodiment, elastic composition can comprise the nano composite material that is formed by the polymer melt blend method.For example, can be with elastomerics and clay composition at any suitable mixing tank such as Banbury ^TMMixing tank, Brabender ^TMBlend in mixing tank or the preferred mixing tank/forcing machine, and will be clay intercalated and peel off and the homodisperse that becomes in polymkeric substance mixes and formation intercalation thing under with the shearing condition that forms nano composite material until being enough under the temperature of 300 ℃ scope to make at 120 ℃.

[0099] in another embodiment, nano composite material can form by emulsion process.For example, this emulsion can form by conventional emulsion technology, that is to say to make hydrocarbon, water and if the surfactant mixtures of using is subjected to sufficient shearing, as one period that is enough to form emulsion in commercial agitator or its coordinator, for example, usually at least several seconds.Can be so that emulsion keeps emulsion form, be with or without successive or mixing or stirring intermittently, have or not heating or the control of other temperature, keeping one section is enough to improve the time that clay peels off, for example 0.1 to 100 hour in one embodiment or more than, or from 1 to 50 hour in another embodiment, or 2 to 20 hours.

[0100] useful cats product comprises tertiary amine, diamines, polyamines, amine salt and quaternary ammonium compound.Useful nonionic surface active agent comprise alkylethoxylate, straight-chain alcohol ethoxylate, alkyl glucoside, acid amides ethoxylate, amine ethoxylate (for example cocoyl-, the tallow base-and oil base-amine ethoxylate), phenol ethoxylate and nonyl phenol ethoxylate.Surfactant concentration is normally allowed the concentration that forms metastable emulsion; In preferred embodiments, the amount of used tensio-active agent is the 0.001wt% at least of total emulsion, more preferably arrives in about 3wt% scope 0.001, and most preferably arrives in the 2wt% scope 0.01.

[0101] in other embodiments, nano composite material can and form by the solution mixing.For example, nano composite material can be produced in the following way: the solution A that will comprise solvent (this solvent comprises hydrocarbon) and at least a layered fillers or clay contacts with at least a elastomeric solution B with comprising solvent, and solvent is removed to form nano composite material from the product of contact of solution A and solution B.Laminated clay can use swelling/exfoliant to handle.In another embodiment, nano composite material prepares by such method, and this method comprises at least a elastomerics is contacted at least a or multiple solvent with at least a layered fillers; And solvent (one or more) removed from product to form nano composite material.In another embodiment, nano composite material is by a kind of method preparation that forms product of contact, this method comprise at least a layered fillers disperseed and then with at least a elastomerics at solvent or comprise in the solvent mixture of at least two kinds of solvents and dissolving; And from product of contact, remove solvent mixture to form nano composite material.

[0102] in the solution blending means, solvent can exist in 30 to 99wt% the scope based on the composition gross weight, and perhaps 40 to 99wt%, perhaps 60 to 99wt%, perhaps 80 to 99wt%, perhaps 90 to 99wt% scope, perhaps 95 to 99wt%.

Filler and additive

[0103] this elastic composition also can comprise other component and the additive that is generally used for the rubber compounding material, for example other processing aid of significant quantity, pigment, promotor, crosslinked and vulcanizing material, antioxidant, antiozonidate and/or filler.Except HPA, elastic composition can be chosen the processing aid that comprises that other is useful wantonly, for example plastomer, polybutene or its mixture.

[0104] elastic composition can be chosen wantonly and comprise at least a filler, for example, and lime carbonate, titanium dioxide, aluminum oxide, zinc oxide, starch, wood chip, carbon black, mica, silicon-dioxide, talcum or its mixture.Filler can be a virtually any size, and the scope that for example generally arrives about 100 μ m at tire industry at about 0.0001 μ m.

[0105] in some embodiments, elastic composition can comprise the talcum of nano-scale.The talcum of nano-scale is compared with the sized talc platelets of stock size has very high surface-area.The talcum of nano-scale generally has 100 to the interior overall dimension of 200nm scope.

[0106] as used herein, silicon-dioxide is intended to refer to silicon-dioxide or the another kind of silica derivative or the silicic acid of any kind or granularity, it is handled by solution, pyrolysis or other similar approach, comprises untreated, precipitated silica, crystalline silica, colloidal silica, pure aluminium silicate or Calucium Silicate powder, pyrogenic silica etc.Precipitated silica can be conventional silicon-dioxide, partly highly dispersible silicon-dioxide or highly dispersible silicon-dioxide.

[0107] in one embodiment, one or more silane coupling agents are used for elastic composition.When silicon-dioxide is main stuffing or combine with another kind of filler when existing, coupling agent caters to the need especially, because they help silica bound to elastomerics.Coupling agent can be a difunctionality organosilane linking agent." organosilane linking agent " is any silane coupled filler and/or activator of crosslinking and/or the silane toughener that those skilled in the art know, including, but not limited to vinyltriethoxysilane, vinyl-three-('beta '-methoxy oxyethyl group) silane, methacryloxypropyl trimethoxy silane, gamma-amino-propyl-triethoxysilicane, γ sulfydryl propyl trimethoxy silicane etc. and composition thereof.

[0108] filler can be carbon black or modified carbon black.Filler can also be the mixture of carbon black and silicon-dioxide.In one embodiment, elastic composition comprises the booster stage carbon black with the content of 10 to 100phr scopes of mixture, more preferably 30 arrives in the 80phr scope in another embodiment, and arrives in the scope of 80phr 50 in another embodiment.The useful rank of sooty comprises the scope from N110 to N990, preferred N660.

Linking agent, vulcanizing agent, sulfuration combination and vulcanization process

[0109] elastic composition and the goods that made by those compositions are usually by means of at least a sulfuration combination, at least a vulcanizing agent, at least a linking agent and/or make elastic composition sulfurized process and prepare.As used herein, at least a sulfuration combination refer to can be as common sense in the industry give any material or the method for curability to rubber.

[0110] common, polymeric blends is crosslinked to improve the mechanical property of polymkeric substance.The physicals of vulcanized rubber mixing material, performance characteristics and weather resistance known with vulcanization reaction during the crosslinked quantity (cross-linking density) that forms relevant with type.Polymeric blends can be by adding vulcanizing agent, for example sulphur, metal, metal oxide such as zinc oxide, superoxide, organometallic compound, radical initiator, the common reagent of lipid acid and other this area and crosslinked.Spendable other known vulcanization process comprises the heat or the radiation-initiated crosslinking of peroxide vulcanizing system, resin cure system and polymkeric substance.Also promotor, activator and retarding agent can be used for sulfidation.

[0111] said composition can be vulcanized (sulfuration) by any suitable method, as making them be subjected to heat or radiation according to any conventional sulfuration process.Heat that needs or radiating amount are to require to carry out the sulfurized amount in composition, and the present invention of this paper is not subjected to the method and the restriction that needs heat of vulcanising composition.Generally, vulcanize in one embodiment at about 100 ℃ and under the temperature of about 250 ℃ scope, carry out, or, carried out about 1 to 150 minute in another embodiment at 150 ℃ to 190 ℃.

[0112] halogen-containing elastomerics can come crosslinked by the reaction of they and metal oxide.Metal oxide can use separately or with its respective metal lipid acid title complex (for example Zinic stearas), or be used in combination with the organic and lipid acid of independent adding such as stearic acid and optional other vulcanizing agent such as compound, alkyl peroxide compound, the diamines or derivatives thereof of sulphur or sulphur.

[0113] sulphur is the most general chemicure agent that is used to contain diene elastomer.It exists as rhombic 8-unit's ring or amorphous polymeric form.Sulfur vulcanization system can be made up of activator, the promotor of activation sulphur and the retarding agent that helps to control vulcanization rate.Activator is by at first forming the chemical that rubber solubility title complex (it forms with reaction of Salmon-Saxl and vulcanizes (sulfurating) reagent then) improves vulcanization rate with booster response.The promotor of general categories comprises amine, diamines, guanidine, thiocarbamide, thiazole, thiuram, sulfinyl amine, sulfenimide, thiocarbamate, xanthogenate etc.

[0114] promotor helping, control that sulfurized begins and vulcanization rate, and the crosslinked quantity and the type that form.Retarding agent can be used for postponing sulfurized begins at first to allow that time enough processes unvulcanized rubber.

[0115] promotion of sulfuration process can be controlled by the amount of regulating promotor (it is organic compound normally).The promotion sulfurized mechanism of natural rubber, BR and SBR relates to complex interactions between vulcanizing agent, promotor, activator and the polymkeric substance.Ideally, in forming effectively crosslinked (it combines two polymer chains and has improved the bulk strength of polymeric matrix), all available vulcanizing agents are consumed.Various promotor are known in the prior art, include but not limited to following material: stearic acid, vulkacit D (DPG), tetramethyl-thiuram disulfide (TMTD), benzothiazyl disulfide base (MBTS), the N-tertiary butyl-2-[4-morpholinodithio sulfinyl amine (TBBS), N-cyclohexyl-2-[4-morpholinodithio-sulfinyl amine (CBS) and thiocarbamide.

[0116] in one embodiment, at least a vulcanizing agent exists with 0.2 to 10phr or 0.5 to 5phr scope, or in another embodiment in 0.75phr arrives the scope of 2phr.

Processing

[0117] elastic composition can come compounding (mixing) by the known any ordinary method of those skilled in the art.This mixing can take place in one step or in a plurality of steps.For example, generally composition was mixed at least two stages, promptly follow at least one unproductive stage of a productivity mix stages.Generally last vulcanizing agent is mixed in the final stage of so-called " productivity " mix stages.In the productivity mix stages, mix generally under the temperature of the mixing temperature that is lower than previous nonproductive mix stages (one or more) or outlet temperature and carry out.Usually with elastomerics, polymeric additive, silicon-dioxide and silicon-dioxide coupling agent with if the carbon black that uses mixes in one or more unproductive mix stages.Term " unproductive " and " productivity " mix stages are that to have personnel of rubber mix field technical ability known.

[0118] in one embodiment, carbon black was added in the stage different with promotor with zinc oxide and other vulcanization activators.In another embodiment, antioxidant, antiozonidate and the work material stage after carbon black is processed with elastomerics is added, and in the end the stage adds with maximization mixing material modulus with zinc oxide.In other embodiments, the other stage can relate to the adding that increases progressively of one or more fillers.

[0119] in another embodiment, the mixing of component can be passed through at any suitable mixing equipment as the mill of two-roller, Brabender ^TMBanbury mixer, has the Banbury of tangent rotor ^TMIn Banbury mixer, Krupp Banbury mixer or the preferred mixing tank/forcing machine elastomeric component, filler and clay are undertaken by method combination well known in the prior art with the rotor that intermeshes.In one embodiment, mixing can carried out under the temperature of the fusing point of the elastomerics (one or more) that is used for composition, or in another embodiment from 40 ℃ to 250 ℃, or in another embodiment from 100 ℃ to 200 ℃.Mixing usually to be enough to making clay peel off and to carry out under the shearing condition of homodisperse with the formation nano composite material in elastomerics (one or more).

[0120] general, elastomerics with 70% to 100% or multiple elastomerics at first mixed 20 to 90 seconds, or reached 40 ℃ to 75 ℃ up to temperature.Then, if generally the elastomerics of about 75% filler and the surplus that has is added mixing tank, and mix and continue to reach 90 ℃ to 150 ℃ up to temperature.Next, remaining filler and processing aid are added, and depend on that used mixed with polymers continues to reach 130 ℃ to 190 ℃ up to temperature.In the time can adding vulcanizing agent, masterbatch mixture by compressing tablet in mill and make cooling for example to 60 to 100 ℃ finish.

[0121] carries out with mixing of clay, wherein in one embodiment clay is added polymkeric substance simultaneously at the adding sooty by the procedure known to those skilled in the art.Generally the HPA processing aid has been reached abundant dispersion back adding in the later stage of mixing period at carbon black and clay in elastomeric matrices.

[0122] vulcanising composition can comprise various elastomericss and the filler with HPA processing aid.Elastic composition generally comprises C ₄To C ₇Monoolefm elastomer, as the elastomerics based on iso-butylene, or preferred halogenation poly-(iso-butylene-altogether-p-methylstyrene), HPA (one or more) exists with 5 to 50phr scope in one embodiment, or 10 to 40phr, or arrive in the 30phr scope 10 in another embodiment.

[0123] can elastomerics and various other rubber disclosed herein or plastics, particularly thermoplastic resin such as nylon or polyolefine such as polypropylene or the polypropylene copolymer mixing based on iso-butylene of the present invention will be can be used for.These compositions can be used for air shield such as air bag, tube, tire flap, casing air (as in air cushion shock absorber), barrier film, and other application that wherein needs high air or oxygen to keep.In one embodiment, the sulfurized composition has at 40 ℃ of following 220cc*mm/[m ²-day] or littler permeability coefficient, or 200cc*mm/[m ²-day] or littler, 160cc*mm/[m ²-day] or littler, or 140cc*mm/[m ²-day] or littler, or 120cc*mm/[m ²-day] or littler, or 100cc*mm/[m ²-day] or littler.In preferred embodiments, the sulfurized elastic composition has at 40 ℃ of following 90cc*mm/[m ²-day] or littler permeability coefficient, or 80cc*mm/[m ²-day] or littler, or 75cc*mm/[m ²-day] or littler, or 70cc*mm/[m ²-day] or littler.

[0124] in one embodiment, the air shield can be by comprising C ₄To C ₇The random copolymers of isomonoolefin derived units, at least a filler, at least a HPA, clay and at least a vulcanizing agent combination; And the component of vulcanization bond and making.

[0125] aforesaid elastic composition can be used to make air film as being used to produce the liner and the inner tube of a tyre of tire.The method and apparatus that is used to make liner and tire is known in this area.The present invention is not restricted to any concrete grammar of making goods such as liner or tire.

Industrial applicibility

[0126] elastic composition can be extruded, compression molding, blowing molding, injection-molded and be laminated to various formed article, comprise fiber, film, laminate, stratiform thing, industrial part such as motor vehicle component, device housings, the consumer's goods, packing etc.

[0127] particularly, elastic composition can be used for the goods of various tire applications such as truck tire, motor bus tire, doughnut, motorcycle tyre, off-the-highway tire, plane tyre etc.Such tire can pass through the known the whole bag of tricks construction of those skilled in the art, shaping, molded and sulfuration.Elastic composition can be fabricated to the parts of finished product or finished product such as the liner of tire.These goods can be selected from air shield, air diaphragms, film, stratiform thing (microbedding and/or multilayer), liner, the inner tube of a tyre, casing air, tire curing air bag etc.

[0128] elastic composition of the present invention can be used for various application, particularly Pneumatic tire assembly, flexible pipe, belt such as travelling belt or automobile belt, solid tyre, footwear component, is used for roller, vibration insolation means, medical device, tackiness agent, wadding, sealing agent, glass assembling mixture, protective coating, air cushion, air cushion spring, bellows, the battery pack that graph technology uses and is used for that fluid keeps and the air bag of sulfuration process.

[0129] elastic composition also can be used for the molded rubber parts, and can obtain widespread use aspect automobile hanging snubber, auto exhaust support and vehicle body anchor.In other was used, elastomerics of the present invention (one or more) or elastic composition also can be used for medical usage such as medicine plug and are used for the closure member and the coating of medical device.

[0130] elastic composition of the present invention is specially adapted to the material of the air retention (capacity) that the tire flap and the inner tube of a tyre and other require.Impermeable tire flap with improvement can be allowed the inflation pressure that keeps suitable; Owing to reducing tire drag, better inflation pressure reservation reduces fuel consumption thus; Because the long tyre life that better tyre tread imprint and more smooth polishing machine cause; And because the better more smooth manipulation response of inflation pressure reservation.

Embodiment

[0131] further describes the elastic composition that comprises elastomerics, HPA and clay referring now to following non-limiting example.

[0132] may the time, standard A STM test is used to measure the physicals of sulfuration mixing material.Stress/strain character (for example tensile strength, elongation at break, modulus value, energy-to-break) is at room temperature used " Die-C " to utilize Instron 4202 according to ASTM D412 and is measured.Stretching strength measurement carries out at ambient temperature; Sample (dog-bone (dog-bone) shape) has the Max. Clearance _M. of 6mm and the limited length of 33mm between two marks.Although the thickness of test sample is nominal 2.00mm, sample thickness has difference, and manually measures by the Mitutoyo Digimatic Indicator that is connected to system computer.The pinblock speed of sample with 500mm/min is stretched, and record stress/strain data.Mean stress/the strain value of at least three samples of record.The error (2 σ) that stretches in measuring is ± 0.47MPa.The error (2 σ) of measuring 100% modulus is ± 0.11MPa; The error (2 σ) of measuring elongation is ± 13%.

[0133] vulcanizing properties adopts from Alpha Technologies, and the MDR 2000 of Inc. measures according to ASTM D 5289 under indicated temperature and under the 0.5 degree arc.Value used herein " MH " and " ML " refer to " peak torque " and " minimal torque " respectively." MS " value is a mooney scorch value, and " ML (1+8) " value is the Mooney viscosity value of polymkeric substance, and " ML (1+4) " value is the Mooney viscosity value of composition.Error (2 σ) during mooney viscosity is measured is ± 0.65." Tc " value be in minute curing time, and " Ts " is minute the time of scorch of meter.

[0134] perviousness adopts Mocon OxTran model 2/61 oxygen permeability testing apparatus to measure.Oxygen permeability is measured by the principle of the dynamic measurement of film transmission according to oxygen.The mixing material sample is sandwiched diffusion cell.The about 5.0cm of sample diameter and thick about 0.5mm.Then residue oxygen is cleaned with the high purity nitrogen carrier gas in this pond.Then nitrogen is led to transmitter up to setting up stable null value.Measure and generally under 40 ℃, carry out.Then purity oxygen is introduced the chamber outside of diffusion cell.To be delivered to the container of measurement oxygen diffusion rate by sample diffusion to the oxygen of internal chamber.Oxygen diffusion rate is represented with the transmitance coefficient.Permeability coefficient is the sample (m that measures and be expressed as per unit area in discrete time unit (for example 24 hours) for the standardized transmitance of thickness of sample (mm) ²) gas volume (cc), and have the cc*mm/ (m of unit ²-day).Permeability coefficient has been considered barometric point and has been expressed as cc*mm/ (m ²-day-mmHg).

[0135] molecular weight of hydrocarbon polymer additives is by gel permeation chromatography measurement.The technology that is used to measure molecular weight (Mn, Mw and Mz) and molecular weight distribution (MWD) is described in U.S. Patent No. 4,540 roughly, in 753, it is hereby incorporated by.(PDI) calculates as Mw/Mn with heterogeneity index.The melt viscosity of hydrocarbon polymer additives is used the Brookfield viscometer with the rotating shaft of " J " type to press ASTM D-6267 and is measured.

[0136] used enumerating of various testing method sees Table 1.The enumerating of various components that is used for embodiment sees Table 2.

Table 1-testing method

Various components in the table 2-elastic composition

Component brief description merchandise resources

EXXPRO ^TMPoly-(the iso-butylene-altogether-of MDX bromination to methyl ExxonMobil Chemical Co.

03-1 vinylbenzene), and 0.85 ± 0.1mol% (Houston, TX)

Benzyl Br; 10 ± 0.5 pairs of methylbenzene

Ethene, the 27-37 mooney viscosity

The N660 carbon black

Cloisite Na ⁺Clay Southern Clay Products

STRUKTOL ^TM40 MS aliphatic-aromatic-cycloalkanes family tree Strucktol Co.of America

The composition of fat (Stow, OH)

Tg＝50℃

Oppera ^TM103J comprises Dicyclopentadiene (DCPD) and methyl is got ExxonMobil Chemical Co.

For the HPA of Dicyclopentadiene (DCPD) (Houston, TX)

CALSOL ^TM810 naphthenic oil R.E.Carroll, Inc. (Trenton,

ASTM103 type NJ)

SP-1068 bromination alkyl phenolic resin Schenectady, Inc.

Tg＝40℃ (Schenectady，NY)

Triethylamine

Stearic acid activator ACI 5106NF, Witco

Manufacturing

Zinc oxide (Zn) activator KADOX ^TM911, Zinc Corp.of

America(Monaca，PA)

MBTS promotor; 2-mercaptobenzothiazole two R.T.Vanderbilt (Norwalk, CT)

Sulfide or Elastochem (Chardon, OH)

Sulfur vulcanization agent Rubbermakers Sulfur

[0137] in an embodiment, model tire flap mixing material adopts the preparation of Banbury mixing tank.Unproductive (fs) mixed cycle is carried out with the mixing tank rotor speed that is set in 70rpm and percussion hammer pressure and 70 ℃ of chamber temps of 60psi.With elastomerics, clay (only mixing material A2, B7 and B9), or clay/triethylamine (TEA) paste (only mixing material A3-A7, B8 and C10) and HPA add in unproductive mixed cycle.In comprising the mixing material of TEA, TEA was directly added in the dry sodium clay before mixing formation clay/TEA paste.Reduce percussion hammer pressure, after 120 seconds remaining fs composition is added excessively.The mixing material temperature is increased to 160 ℃ and formulation mixed 300 seconds.

[0138], the Banbury mixing tank is set at 30-40rpm mixing velocity, 50psi percussion hammer pressure and 60 ℃ of chamber temps in subordinate phase (productivity) mixed cycle.With the fs mixing material half and the subordinate phase composition is mixed together and then remaining fs mixing material was added before reducing percussion hammer.Then mixing material was mixed 90 seconds.Then mixing material by being added, mixing material is kept the refrigerative mixing roll and compressing tablet on 2-roller mixing roll.Banbury mixing mixing material temperature decline in order to unproductive and productivity stage is respectively 160 ℃ and 105 ℃.

Embodiment 1

[0139] prescription that is used for model tire flap mixing material of embodiment 1 is listed in table 3, and all listed consumptions are in phr.Mixing material A1 represents comparative formula.In mixing material A2, the sodium clay is added comparative formula.Mixing material A3, A4 comprise clay/TEA paste with A5 with different amounts.The various processing of test mixing material, sulfuration and physicals.Data are listed in the table 4.

Table 3-model tire flap prescription

The character of table 4-model tire flap mixing material

[0140] adding of sodium clay in the comparative formula of mixing material A1 improved the pressuretightness of mixing material among the mixing material A2, and other mixing material character to test has little effect or not influence simultaneously.Believe that the only minimum change of finding out is because the ionic sodium clay distributes and disperses bad in nonpolar elastomeric polymer in mixing material character.Further believe when clay more fully distributes and be dispersed in the elastomerics as can be seen owing to comprise the bigger influence of the mixing material character of clay.

[0141] under low TEA level (mixing material A3,0.05phr TEA), the pressuretightness of mixing material is similar with the mixing material (mixing material A2) that contains the sodium clay.Yet, loading level (mixing material A4 and A5) at higher TEA, the pressuretightness comparison of mixing material is than poorer (being that mixing material A4 and A5 are more permeable) of prescription (mixing material A1).

[0142] in mixing material A3, A4 and A5, adds some character that TEA has influenced mixing material really.In addition, influence size is corresponding with the TEA contents level.Mooney viscosity is higher in the mixing material of the TEA load that higher level is arranged.Believe that the mooney viscosity increase with the TEA load that increases is because the quantity in ammonium site increase on the elastomeric polymer.

[0143] in addition, the existence of TEA, especially with under the high capacity level has significantly reduced mooney scorch value.This shows that TEA may cause the undesirable scorching of mixing material.

Embodiment 2

[0144] in embodiment 2, (be Calsol with the cycloalkanes treated oil of comparative formula (mixing material A1) ^TM810) replace with HPA.In mixing material B1, adopt the treated oil of the HPA replacement 8phr of 25phr.In mixing material B2, also added the sodium clay and in mixing material B3, sodium clay/TEA paste has been added mixing material.The prescription that is used for mixing material is listed in table 5, and all consumptions of listing are in phr.Test mixing material a series of character obtains that the results are shown in Table 6.

Table 5-contains the model tire flap mixing material of HPA

Table 6-contains the character of the model tire flap mixing material of HPA

[0145] replace the cycloalkanes treated oil that hardness, stretching and the tear resistance of model tire flap had seldom influence with HPA.The MDR of mixing material is lower than those of embodiment 1 among the embodiment 2, and this may show that vulcanization rate is slower.Yet vulcanization rate can be regulated by changing the sulfuration combination, as passing through to use different promotor.

[0146] mooney viscosity that comprises the mixing material of HPA is lower than the mooney viscosity of model mixing material among the embodiment 1.Yet still in desirable scope for processing characteristics, it is 50-60MU to mooney viscosity.In addition, the mooney scorch value of mixing material is slightly high among the embodiment 2, shows that the mixing material that comprises HPA may have better sulfuration stability.

[0147] replace the cycloalkanes treated oil to greatly reduce the perviousness of mixing material with HPA.Permeability coefficient 150cc*mm/ (m ²-sky) mixing material A1 and permeability coefficient 87cc*mm/ (m ²-sky) mixing material B1 comparison shows that, has reached the improvement of mixing material perviousness 42% when replacing the cycloalkanes treated oil with HPA.In addition, adding the sodium clay in mixing material B2 passes through permeability coefficient from 87cc*mm/ (m ²-sky) (mixing material B1) is reduced to 67cc*mm/ (m ²-day) (mixing material B2) and improve the pressuretightness of mixing material.This reflects that further comparing impermeable 55% with mixing material A1 improves.

[0148] replace the cycloalkanes treated oil to produce the mixing material that perviousness is improved 40-50% with HPA, simultaneously if not better also kept and similar machinery of the prescription of mixing material A1 and physicals.The liner prescription that further adding of sodium clay is comprised HPA has produced even further pressuretightness improvement, has kept the acceptable machinery and the physicals of mixing material simultaneously.

Embodiment 3

[0149] in embodiment 3, the model tire flap mixing material of test implementation example 1 prescription wherein replaces cycloalkanes treated oil (being Calsol 810) and phenolic tackifying resins (being SP1068) with HPA.The tire mixing material prescription that is used for embodiment 3 is listed in table 7, and all listed consumptions are in phr.The mixing material A1 of embodiment 1 represents general tire flap mixing material prescription.In mixing material C1, the HPA of use 29phr replaces treated oil and the resol of the 12phr among the mixing material A-1.Mixing material C2 is identical with mixing material C1, but also comprises the TEA of 0.1phr.The a series of processing of test mixing material, sulfuration and physicals, the data that obtain are listed in the table 8.

Table 7-comprises the tire flap prescription of HPA

Table 8-comprises the character of the tire flap mixing material of HPA

[0150] replacing cycloalkanes treated oil and phenolic tackifying resins to produce character with HPA is similar to reference mixing material A1 and is similar to those the mixing material of finding when only replacing treated oil in embodiment 2.The mixing material mechanical property of mixing material A1, C1 and C2 such as tensile strength and hardness are all in the manufacturing objective scope of the requirement that is used for the tire flap mixing material.The general aspects that is used for the tire flap mixing material comprises that tensile strength arrives in the 11MPa scope 9, elongation at break about 700 to 900%, and mooney viscosity (ML1+4) about 50 to 70MU, referring to people " Advances in Tire Innerliner Technologies, " such as for example Brendan Rodgers Rubber World, the 234th volume, No. 3,36-41 page or leaf (in June, 2006) is hereby incorporated by.

[0151] yet, in mixing material C1 and C2, wherein cycloalkanes treated oil and phenolic tackifying resins all replace with HPA, the too low and energy measurement not of mooney scorch value.This shows and has such possibility: these mixing materials can vulcanize prematurely.Therefore, HPA may not be the suitable surrogate of resol, and this is because there be not obviously reduction of sulfuration stability under the situation of resol.

[0152] yet, when replacing phenolic tackifying resins and cycloalkanes treated oil with HPA in mixing material C2, oxygen permeability coefficient is reduced to 72cc*mm/ (m ²-day).This compares with mixing material A 1 is infiltrative 50% reduction.This also represent with permeability coefficient until 220cc*mm/ (m ²Almost 60% reduction of typical brominated butyl rubber tire flap mixing material phase specific permeability-sky) is referring to people " Advances in Tire InnerlinerTechnologies, " such as for example Brendan Rodgers Rubber World, the 234th volume, No. 3,36-41 page or leaf (in June, 2006).

[0153] in mixing material C2, when TEA is added this prescription, reached similar hyposmosis coefficient.TEA is considered to promote better montmorillonite clay to disperse.The tire flap mixing material (being with or without TEA) that comprises HPA has obtained significantly better pressuretightness (promptly lower permeability coefficient), and keeps the mixing material mechanical property of other requirement simultaneously.

[0154] all patent and patent application, test method (as ASTM method, UL method etc.) and other files of quoting in this article all are incorporated herein by reference, and are all authorities that allow up to such open and the inconsistent degree of the present invention and wherein such combining.

Go up in limited time with numeral when this paper lists digital lower limit, the scope from any lower limit to any upper limit is also design.Though described exemplary embodiment of the subject disclosure especially in detail, when being understood that, various other changes are conspicuous to those skilled in the art and can be made by them under the situation that does not depart from spirit and scope of the invention.Therefore, the scope of not wishing appended claim is confined to the description that embodiment and this paper illustrate in this, but claim is regarded as comprising the feature that is present in all novelties that can patent of the present invention, and the technician who comprises the technical field of the invention thinks all features of Equivalent.

Claims (15)

1. sulfurized elastic composition, it comprises:

A) at least a C ₄-C ₇Monoolefm elastomer;

B) hydrocarbon polymer additives, wherein hydrocarbon polymer additives comprises the ring-type component; And

C) clay;

Wherein, said composition has at 40 ℃ of following 90cc*mm/ (m ²-day) or littler permeability coefficient.

2. the composition of claim 1, wherein hydrocarbon polymer additives exists to the scope of 40phr with 10phr.

3. claim 1 or 2 composition, wherein elastic composition further comprises one or more filler components that is selected from following material: lime carbonate, mica, silicon-dioxide, silicate, talcum, titanium dioxide, starch, wood chip, carbon black and composition thereof.

4. each composition of claim 1 to 3, wherein this clay be peel off and be selected from following group: the natural or synthetic polynite of peeling off, nontronite, beidellite, volkonskoite, LAPONITE, hectorite, saponite, sauconite, magadiite, fibrous morphology crystals, lucianite, vermiculite, halloysite, aluminate oxide compound, hydrotalcite and composition thereof.

5. each composition of claim 1 to 4, wherein elastic composition is substantially free of naphthenic oil.

6. each composition of claim 1 to 5, wherein hydrocarbon polymer additives comprises the ring-type component of 75wt% at least.

7. each composition of claim 1 to 6, wherein hydrocarbon polymer additives comprises Dicyclopentadiene (DCPD).

8. each composition of claim 1 to 7, wherein hydrocarbon polymer additives has at about 115 softening temperatures in about 130 ℃ of scopes.

9. each composition of claim 1 to 8, wherein hydrocarbon polymer additives have about 500 in the 700g/mol scope Mw and the Tg in about 65 to 75 ℃ of scopes.

10. each composition of claim 1 to 9, wherein said composition is air shield, tire flap, the inner tube of a tyre or flexible pipe.

11. air shield that comprises by the elastic composition of following method preparation:

A) in conjunction with at least a based on C ₄-C ₇The elastomerics of monoolefine, at least a filler, at least a clay and at least a hydrocarbon polymer additives, wherein hydrocarbon polymer additives comprises ring-type component and at least a vulcanizing agent; With

B) component of vulcanization bond.

12. the air shield of claim 11, wherein this air shield is tire flap, the inner tube of a tyre or flexible pipe.

13. the air shield of claim 11 or 12, wherein this clay is to be selected from following exfoliated clay: the natural or synthetic polynite of peeling off, nontronite, beidellite, volkonskoite, LAPONITE, hectorite, saponite, sauconite, magadiite, fibrous morphology crystals, lucianite, vermiculite, halloysite, aluminate oxide compound, hydrotalcite and composition thereof.

14. each air shield of claim 11 to 13, wherein hydrocarbon polymer additives comprises the ring-type component of 75wt% at least.

15. each air shield of claim 11 to 14, wherein hydrocarbon polymer additives has at about 115 softening temperatures in about 130 ℃ of scopes.